Diphenylamine compounds, polymers prepared therefrom and non-linear optics devices containing the same

ABSTRACT

Diphenylamines of the formula ##STR1## where the ring A can be benzo-fused, and 
     D is aryl or a five-membered aromatic heterocyclyl which contains one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, in the heterocyclic ring and can be fused to a benzene, thiophene, pyridine or pyrimidine ring, 
     X is N═N or, if D is aryl, is alternatively CH═CH, or D--X together is 1,2,2-tricyanovinyl, 
     R 1 , R 2 , R 3  and R 4  are each hydrogen, C 1  -C 6  -alkyl, C 1  -C 6  -alkoxy or halogen, 
     R 5  is prop-1-en-3-yl, acryloyl or methacryloyl, 
     R 6  and R 7  are each hydrogen, C 1  -C 6  -alkyl, C 1  -C 6  -alkoxy, halogen, prop-1-en-3-yl, acryloyl, methacryloyl or oxiranylmethoxy, and 
     Y is C 1  -C 20  -alkylene, 
     polymers derived from the compounds, and their use in non-linear optics.

The present invention relates to novel diphenylamines of the formula I##STR2## where the ring A can be benzo-fused, and

D is aryl or a five-membered aromatic heterocyclyl which contains one tothree hetero atoms selected from the group consisting of nitrogen,oxygen and sulfur, in the heterocyclic ring and can be fused to abenzene, thiophene, pyridine or pyrimidine ring,

X is N═N or, if D is aryl, is alternatively CH═CH, or D--X together is1,2,2-tricyanovinyl,

R¹, R², R³ and R⁴, independently of one another, are each hydrogen, C₁-C₆ -alkyl, C₁ -C₆ -alkoxy or halogen,

R⁵ is prop-1-en-3-yl, acryloyl or methacryloyl,

R⁶ and R⁷, independently of one another, are each hydrogen, C₁ -C₆-alkyl, C₁ -C₆ -alkoxy, halogen, prop-1-en-3-yl, acryloyl, methacryloylor oxiranylmethoxy, and

Y is C₁ -C₂₀ -alkylene,

to polymers derived from the novel compounds, and to their use innonlinear optics.

DE-A-4 213 155 describes azo dyes having a diazo component from theaniline series and a coupling component from the N-benzyl- orN-phenylethylaniline series, homopolymers or copolymers thereof, andtheir use in nonlinear optics.

Furthermore, Angew. Chem., 96 (1984), 637 to 651, discloses the use ofstilbene derivatives or specific azo dyes for this purpose.

It is an object of the present invention to provide novel compoundsbased on stilbene derivatives, tricyanovinylbenzenes and aryl- orhetarylazobenzenes or -naphthalenes which are advantageously suitablefor use in nonlinear optical systems. In particular, these compoundsshould have high hyperpolarizability values and should be stable to heatand oxidation. The compounds should also be polymerizable, and thesystems obtained from them should have a high glass transitiontemperature.

We have found that this object is achieved by the diphenylamines of theformula I described in greater detail in the introduction.

Preference is given to diphenylamines of the formula I in which D isaryl or heterocyclyl selected from the series consisting of pyrrolyl,furanyl, thiophenyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl,benzofuranyl, benzothiophenyl, benzimidazolyl, benzoxazolyl,benzothiazolyl, benzisothiazolyl, pyridothiophenyl, pyrimidothiophenyland thienothiazolyl.

Particular preference is given to diphenylamines of the formula I inwhich D is aryl or heterocyclyl from the series consisting of pyrrolyl,thiophenyl, pyrazolyl, thiazolyl, isothiazolyl, triazolyl, thiadiazolyl,benzothiophenyl, benzothiazolyl, benzisothiazolyl, pyridothiophenyl,pyrimidothiophenyl and thienothiazolyl.

Particular importance is attached to diphenylamines of the formula I inwhich

D is ##STR3## where L¹ is nitro, cyano, C₁ -C₆ -alkanoyl, benzoyl, C₁-C₆ -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl or--CH═T, where T is hydroxyimino, C₁ -C₄ -alkoxyimino or a radical of aCH-acidic compound,

L² is hydrogen, C₁ -C₆ -alkyl, halogen, hydroxyl, mercapto,unsubstituted or phenyl- or C₁ -C₄ -alkoxy-substituted C₁ -C₆ -alkoxy,unsubstituted or substituted phenoxy, unsubstituted orphenyl-substituted C₁ -C₆ -alkylthio, unsubstituted or substitutedphenylthio, C₁ -C₆ -alkylsulfonyl or unsubstituted or substitutedphenylsulfonyl,

L³ is cyano, C₁ -C₄ -alkoxycarbonyl or nitro,

L⁴ is hydrogen, C₁ -C₆ -alkyl or phenyl,

L⁵ is C₁ -C₆ -alkyl or phenyl,

L⁶ is hydrogen, cyano, C₁ -C₄ -alkoxycarbonyl, C₁ -C₆ -alkanoyl,thiocyanato or halogen,

L⁷ is nitro, cyano, C₁ -C₆ -alkanoyl, benzoyl, C₁ -C₄ -alkoxycarbonyl,C₁ -C₆ alkylsulfonyl, substituted or unsubstituted phenylsulfonyl or--CH═T, where T is as defined above,

L⁸ is hydrogen, C₁ -C₆ -alkyl, cyano, halogen, unsubstituted or phenyl-or C₁ -C₄ -alkoxy-substituted C₁ -C₆ -alkoxy, unsubstituted orphenyl-substituted C₁ -C₆ -alkylthio, unsubstituted or substitutedphenylthio, C₁ -C₆ -alkylsulfonyl, unsubstituted or substitutedphenylsulfonyl or C₁ -C₄ -alkoxycarbonyl,

L⁹ is cyano, unsubstituted or phenyl-substituted C₁ -C₆ -alkyl,unsubstituted or phenyl-substituted C₁ -C₆ -alkylthio, unsubstituted orsubstituted phenyl, thienyl, C₁ -C₄ -alkylthienyl, pyridyl or C₁ -C₄-alkylpyridyl,

L¹⁰ is phenyl or pyridyl,

L¹¹ is trifluoromethyl, nitro, C₁ -C₆ -alkyl, phenyl, unsubstituted orphenyl-substituted C₁ -C₆ -alkylthio or C₁ -C₆ -dialkylamino,

L¹² is C₁ -C₆ -alkyl, phenyl, 2-cyanoethylthio or 2-(C₁ -C₄-alkoxycarbonyl)ethylthio,

L¹³ is hydrogen, nitro or halogen,

L¹⁴ is hydrogen, cyano, C₁ -C₄ -alkoxycarbonyl, nitro or halogen, and

L¹⁵ is cyano, nitro, hydroxysulfonyl, 2,2-dicyanovinyl,1,2,2-tricyanovinyl or E--N═N, where E is phenyl which is substituted bycyano, nitro, 2,2-dicyanovinyl or 1,2,2-tricyanovinyl, and

R⁶ and R⁷ are each as defined above.

All the alkyl and alkylene groups which occur in the above formulae Iand II may be either straight-chain or branched.

If the above formulae I and II contain any substituted phenyl groups,examples of possible substituents are, unless stated otherwise, C₁ -C₄-alkyl, chlorine, bromine, nitro or C₁ -C₄ -alkoxy. The phenyl radicalshere generally have from 1 to 3 substituents.

If the above formulae I and II contain any substituted alkyl groups,these generally have 1 or 2 substituents.

L², L⁴, L⁵, L⁸, L⁹, L¹¹, L¹², R¹, R², R³, R⁴, R⁶ and R⁷ are, forexample, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

L⁹ may additionally be, for example, benzyl or 1- or 2-phenylethyl.

L², L⁸, L⁹ and L¹¹ may additionally be, for example, methylthio,ethylthio, propylthio, isopropylthio, butylthio, isobutylthio,pentylthio, hexylthio, benzylthio or 1- or 2-phenylethylthio.

L² and L⁸ may additionally be, for example, phenylthio,2-methyl-phenylthio, 2-methoxyphenylthio or 2-chlorophenylthio.

L², L⁸, R¹, R², R³, R⁴, R⁶ and R⁷ may additionally be, for example,methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy,pentoxy, isopentoxy, neopentoxy, tert-pentoxy, hexyloxy or2-methylpentoxy.

L⁶, L², L⁸, L¹³, L¹⁴, R¹, R², R³, R⁴, R⁶ and R⁷ can be, for example,fluorine, chlorine or bromine.

L⁷, L¹, L² and L⁸ can be, for example, methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl,hexylsulfonyl, phenylsulfonyl, 2-methylphenylsulfonyl,2-methoxyphenylsulfonyl or 2-chlorophenylsulfonyl.

L³, L⁶, L⁷, L⁸ and L¹⁴ can be, for example, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,isobutoxycarbonyl or sec-butoxycarbonyl.

L² and L⁸ can additionally be, for example, 2-methoxyethoxy,2-ethoxyethoxy, 2- or 3-methoxypropoxy, 2- or 3-ethoxypropoxy, 2- or4-methoxybutoxy, 2- or 4-ethoxybutoxy, 5-methoxypentoxy,5-ethoxypentoxy, 6-methoxyhexyloxy, 6-ethoxyhexyloxy, benzyloxy or 1- or2-phenylethoxy.

L¹¹ can additionally be, for example, dimethylamino, diethylamino,dipropylamino, diisopropylamino, dibutylamino, dipentylamino,di-hexylamino or N-methyl-N-ethylamino.

L¹² can additionally be, for example, 2-methoxycarbonylethylthio or2-ethoxycarbonylethylthio.

L⁹ can additionally be, for example, phenyl, 2-, 3- or 4-methylphenyl,2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-,3- or 4-chlorophenyl, 2-, 3- or 4-methoxyphenyl, 2- or 3-methylthienylor 2-, 3- or 4-methylpyridyl.

L¹, L⁶ and L⁷ can additionally be, for example, formyl, acetyl,propionyl, butyryl, pentanoyl or hexanoyl.

If L¹ or L⁷ is --CH═T where T is derived from a CH-acidic compound H₂ T,the CH-acidic compound H₂ T can be, for example, a compound of theformula ##STR4## where Z¹ is cyano, nitro, C₁ -C₄ -alkanoyl,unsubstituted or substituted benzoyl, C₁ -C₄ -alkylsulfonyl,unsubstituted or substituted phenylsulfonyl, carboxyl, C₁ -C₄-alkoxycarbonyl, C₃ -C₄ -alkenyloxycarbonyl, phenoxycarbonyl, carbamoyl,C₁ -C₄ -mono- or dialkylcarbamoyl, unsubstituted or substitutedphenylcarbamoyl, unsubstituted or substituted phenyl, benzothiazol-2-yl,benzimidazol-2-yl, 5-phenyl-1,3,4-thiadiazol-2-yl or2-hydroxyquinoxalin-3-yl,

Z² is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₃ -C₄ -alkenyloxy, Z³ is C₁ -C₄-alkoxycarbonyl, C₃ -C₄ -alkenyloxycarbonyl, phenylcarbamoyl orbenzimidazol-2-yl,

Z⁴ is cyano, C₁ -C₄ -alkoxycarbonyl or C₃ -C₄ -alkenyloxycarbonyl,

Z⁵ is hydrogen, C₁ -C₆ -alkyl, C₁ -C₄ -alkenylamino or benzoylamino,

Z⁶ is hydrogen, C₁ -C₄ -alkyl or phenyl,

Z⁷ is oxygen or sulfur, and

Z⁸ is C₁ -C₄ -alkyl.

Special mention should be made here of the radical derived fromcompounds of the formula IIIa, IIIb or IIIc in which Z¹ is cyano, C₁ -C₄-alkanoyl, C₁ -C₄ -alkoxycarbonyl or C₃ -C₄ -alkenyloxycarbonyl, Z² isC₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₃ -C₄ -alkenyloxy, Z³ is C₁ -C₄-alkoxycarbonyl or C₃ -C₄ -alkenyloxycarbonyl, and Z⁴ is cyano.

Very particular mention should be made here of the radical derived fromcompounds of the formula IIIa, IIIb or IIIc in which Z¹ is cyano, C₁ -C₄-alkoxycarbonyl or C₃ -C₄ -alkenyloxycarbonyl, Z² is C₁ -C₄ -alkoxy orC₂ -C₄ -alkenyloxy, Z³ is C₁ -C₄ -alkoxycarbonyl or C₃ -C₄-alkenyloxycarbonyl, and Z⁴ is cyano.

L¹⁵ is, for example, 2- or 4-cyanophenyl, 2- or 4-nitrophenyl, 2- or4-hydroxysulfonylphenyl, 2- or 4-(2,2-dicyanovinyl)phenyl or 2- or4-(1,2,2-tricyanovinyl)phenyl.

Y is, for example, CH₂, (CH₂)₂, (CH₂)₃, (CH₂)₄, (CH₂)₅, (CH₂)₆, (CH₂)₇,(CH₂)₈, (CH₂)₉, (CH₂)₁₀, CH(CH₃)CH₂ or CH(CH₃)CH(CH₃).

Particular mention should be made of diphenylamines of the formula I inwhich D is aryl, thienyl, thiazolyl or thiadiazolyl, where particularmention should be made of radicals of the formulae IIb, IId, IIg andIIp.

Particular mention should furthermore be made of diphenylamines of theformula I in which X is N═N.

Particular mention should furthermore be made of diphenylamines of theformula I in which R¹, R², R³ and R⁴ are each hydrogen.

Particular mention should furthermore be made of diphenylamines of theformula I in which R⁶ and R⁷ are each hydrogen.

Particular mention should furthermore be made of diphenylamines of theformula I in which R⁵ is acryloyl or methacryloyl.

Particular mention should furthermore be made of diphenylamines of theformula I in which Y is C₂ -C₆ -alkylene.

The diphenylamines of the formula I can be prepared by methods known perse.

Compounds of the formula I in which X is N═N can be obtained, forexample, by the methods described in EP 201 896, DE-A 3 108 077, U.S.Pat. No. 4,843,153 or GB-A 1,546,803. For example, an amine of theformula IV

    D--NH.sub.2                                                (IV),

where D is as defined above, can he diazotized and coupled to a couplingcomponent of the formula V ##STR5## where the ring A, R¹, R², R³, R⁴,R⁵, R⁶, R⁷ and Y are each as defined above.

The compounds of the formula I in which X is CH═CH can be obtained, forexample, by the method described in J. Chem. Soc., 1942, 103 to 116. Forexample, aromatic aldehydes can be reacted with phosphorus ylides in aWittig-type reaction.

The compounds of the formula I in which D--X together are1,2,2-tricyanovinyl can be obtained, for example, by the methoddescribed in J. Am. Chem. Soc., 80 (1958), 2815 to 2822.

The present invention furthermore relates to diphenylamine-containingpolymers which contain, as characteristic monomer units, a divalentradical derived from a diphenylamine of the formula I, and radicals ofthe formulae VI, VII and VIII ##STR6## where Q¹ is hydroxyl, C₁ -C₆-alkoxy, oxiranylmethoxy, phenoxy, amino or C₁ -C₄ -mono- ordialkylamino,

Q² is hydrogen or methyl, and

W is C₂ -C₁₀ -alkylene,

where the proportion of monomer units of divalent radicals derived fromthe formula I is from 1 to 100 mol %, that of the formula VI is from 0to 99 mol %, that of the formula VII is from to 99 mol % and that of theformula VIII is from 0 to 75 mol %, in each case based on the polymer,and the mean molecular weight of the polymer is from 1,000 to 500,000.

One divalent radical derived from a diphenylamine of the formula Ipreferably conforms to the formula Ia or Ib ##STR7##

The novel polymers can be prepared by methods known per se, asdescribed, for example, in J. Polymer Sci., Part A, Polymer Chem., 28(1990), 1 to 13.

In an expedient reaction, a corresponding diphenylamine of the formula Iis reacted with an acrylic compound of the formula IX ##STR8## where Q¹and Q² are each as defined above, styrene and a cinnamic ester of theformula X ##STR9## where Q² and W are each as defined above, in theabove molar ratio in an inert solvent (for example toluene or xylene) inthe presence of a free-radical initiator (for exampleazobisisobutyronitrile).

The diphenylamines of the formula I and the polymers containingdiphenylamines of the formula I are advantageously suitable for use innonlinear optics.

The novel compounds are stable to oxidation and have particularly largemolecular hyperpolarizability values (β). In addition, the polymers havea high glass transition temperature and thus high relaxation stability.

The molecular hyperpolarizability can be determined, for example, by thesolvatochromism method (see, for example, Z. Naturforschung 20a (1965),1441 to 1471, or J. Org. Chem., 54 (1989), 3775 to 3778), in which theposition of the absorption band of a compound is determined in varioussolvents. The shift of the absorption band is then directly proportionalto the β value, i.e. compounds having a large solvatochromic shift havelarge molecular hyperpolarizability and are therefore highly suitablefor use in nonlinear optical systems (see, for example, Chemistry andIndustry (1990), 600 to 608).

Particular mention should be made here of the suitability of the novelsubstances in communications technology, electrooptical modulators (e.g.Mach-Zehnder interferometer), optical switches, frequency mixing orwaveguides.

The examples below illustrate the invention in greater detail.

EXAMPLE 1

a) 169.1 g (1 mol) of diphenylamine and 6.76 g (49 mmol) of anhydrouszinc chloride were introduced into a 0.5 l autoclave, and 46.2 g (1.05mol) of ethylene oxide were subsequently injected at 110° C. undernitrogen pressure (maximum pressure 6 atm.). The mixture was thenstirred at 110° C. for 3 hours. When the reaction was complete, thereaction product was distilled under reduced pressure, giving 185.3 g(87%) of a pale yellow oil of the formula (C₆ H₅)₂ NC₂ H₄ OH.

b) 63.9 g (0.3 mol) of the product described under a) were introducedinto 600 ml of methylene chloride and 60 ml of triethylamine. 62.2 g(0.35 mol) of methacryloyl chloride, 40 dissolved in 150 ml of methylenechloride, were added dropwise, and the mixture was stirred at roomtemperature for a further 48 hours. The reaction solution was thenextracted twice with saturated sodium hydrogencarbonate solution, driedover sodium sulfate and evaporated under reduced pressure, 45 giving 69g (88.1%) of a pale oil of the formula

    (C.sub.6 H.sub.5).sub.2 NC.sub.2 H.sub.4 OCOC(CH.sub.3)═CH.sub.2

c) 10 g (0.04 mol) of 4-amino-4'-nitroazobenzene were diazotized bymeans of nitrosylsulfuric acid in 300 ml of 85% strength sulfuric acid.11.2 g (0.04 mol) of the product described under b) in 100 g of ice, 30ml of conc. hydrochloric acid and 80 ml of N,N-dimethylformamide (DMF)were added at 0° C. to this solution. After 1 hour, the pH was adjustedto 4 by means of sodium acetate, and the mixture was stirred for afurther 48 hours. The resultant dye was subsequently filtered off withsuction, washed with water and dried under reduced pressure, giving 6.2g of the dye of the formula ##STR10##

EXAMPLE 2

6.5 g (0.04 mol) of 3,5-dicyano-4-methyl-2-aminothiophene werediazotized at -5° C. by means of nitrosylsulfuric acid in 300 ml of 85%strength sulfuric acid. This solution was added at -5° C. to a solutionof 11.2 g (0.04 mol) of the product described in Example 1b) in 100 g ofice, 30 ml of conc. hydrochloric acid and 80 ml of DMF. After about 1hour, the pH was adjusted to 4 by means of sodium acetate. After afurther 24 hours, the dye was filtered off with suction, washed withwater and dried under reduced pressure, giving 5.8 g of a dye of theformula ##STR11##

EXAMPLE 3

0.04 mol of 4-nitroaniline were diazotized at 0° C. by means ofnitrosylsulfuric acid in 300 ml of 85% strength sulfuric acid. The diazosolution was added at 0° C. to a solution of 11.2 g (0.04 mol) ofN-(6-methacryloyloxyhexyl)diphenylamine, prepared by a method similar tothat of Example 1b, in 100 g of ice, 30 ml of conc. hydrochloric acidand 80 ml of DMF. After about 1 hour, the pH was adjusted to 4 by meansof sodium acetate. The mixture was subsequently stirred for a further 24hours, and the dye was filtered off with suction, washed with water anddried under reduced pressure, giving 8.8 g of a dye of the formula##STR12##

The dyes shown below were obtained similarly.

    __________________________________________________________________________    Ex. No.                                                                           Formula                                                                   __________________________________________________________________________         ##STR13##                                                                5                                                                                  ##STR14##                                                                6                                                                                  ##STR15##                                                                7                                                                                  ##STR16##                                                                8                                                                                  ##STR17##                                                                9                                                                                  ##STR18##                                                                10                                                                                 ##STR19##                                                                11                                                                                 ##STR20##                                                                12                                                                                 ##STR21##                                                                __________________________________________________________________________

We claim:
 1. A diphenylamine of the formula I ##STR22## where the ring Ais an unfused or benzo-fused ring, andD is aryl or a five-memberedaromatic heterocyclyl which contains one to three hetero atoms selectedfrom the group consisting of nitrogen, oxygen and sulfur, in theheterocyclic ring or is further fused to a benzene, thiophene, pyridineor pyrimidine ring, X is N═N; or, if D is aryl, X is N═N, or CH═CH; orD--X together is 1,2,2-tricyanovinyl, R¹, R², R³ and R⁴, independentlyof one another, are each hydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, orhalogen, R⁵ is prop-1-en-3-yl, acryloyl, or methacryloyl R⁶ and R⁷,independently of one another, are each hydrogen, C₁ -C₆ alkyl C₁ -C₆-alkoxy, halogen, prop-1-en-3-yl, acryloyl, methacryloyl oroxiranylmethoxy, and Y is C₁ -C₂₀ -alkylene.
 2. A diphenylamine asclaimed in claim 1, wherein D is aryl or heterocyclyl selected from thegroup consisting of pyrrolyl, furanyl, thiophenyl, pyrazolyl,imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl,oxadiazolyl, thiadiazolyl, benzofuranyl, benzothiophenyl,benzimidazolyl, benzoxazolyl, benzothiazolyl, benzisothiazolyl,pyridothiophenyl, pyrimidothiophenyl and thienothiazolyl.
 3. Adiphenylamine as claimed in claim 1, wherein D is aryl or heterocyclylfrom the group consisting of pyrrolyl, thiophenyl, pyrazolyl, thiazolyl,isothiazolyl, triazolyl, thiadiazolyl, benzothiophenyl, benzothiazolyl,benzisothiazolyl, pyridothiophenyl, pyrimidothiophenyl andthienothiazolyl.
 4. A diphenylamine as claimed in claim 1, wherein X isN═N.
 5. A diphenylamine as claimed in claim 1, wherein R¹, R², R³ and R⁴are each hydrogen.
 6. A diphenylamine as claimed in claim 1, wherein R⁶and R⁷ are each hydrogen.
 7. A diphenylamine as claimed in claim 1,wherein R⁵ is acryloyl or methacryloyl.
 8. In a non-linear optics devicecontaining a Compound having molecular hyperpolarizability, theimprovement wherein the compound having molecular hyperpolarizability isa diphenylamine compound as claimed in claim 1.